Monazo pyrazolone dye



Patented Dec. 31 19 29 1,741,418

TATES FFICE KENNETH H. 00m F BUFFALO, NEW YORK, ASSIGNR Til) NATIONAL ANIL INE & GEM-e3 (70., DIG, OF NEW YORK, N. Y., A. GORPQRATWON @F NEW YORK uoiuzo r T-QLONE are We Drawing. Application filed October 9, 1925. Berle! No. 61,589.

This invention relates to the production of aminonaphtholl-sulfonic acid are slowly innew monazo pyrazolone dyes which are of troduced into a well-stirred solution at a temvalue for dyeing wool and other material, as perature of -25 C. of 55.5 parts (in well as for the formation of valuable lakes or slight excess of one mol) of the sodium salt 5 pigments. Material dyed or printed with the of l-(3-su1fopheny1)-3-methyl-5-pyrazolone new dyestuffs also form a part of the present in 1000 parts water containing a suiiicient invention. v quantity of sodium carbonate to maintain an The new dyes may be obtained by coupling alkaline reaction throughout the combinaone molecular proportion of the diazo comtion. When the combination is completed, 10 pound derived from an orthoaminonaphthol which requires a few hours, the solution is sulfonic acid, more particularly the 1.2 and heated to about 60-65 (l, acidified by the 2.1-aminonaphthol sulfonic acids, and esaddition of a slight excess of hydrochloric pecially 1.2-aminonaphtholl-sulfonic acid, acid, and salted out b the addition of comwith one molecular proportion of a 1-(3- mop salt, cooled to a cut 40 0., and then suliophenyl)-5-pyrazolone capable of comfiltered off, pressed and dried in the usual bining in position four and which may conmanner. tain halogen substituted in the phenyl The product thus obtained and which'correnucleus. I sponds with the probable formula The'new dyestufi's thus obtained correspond with the general formula wherein R signifies a 1-(3'-su1fophenyl)-3 methyl or carboxyl-5-pyrazolone nucleu comhined in position four with the azo br1dge,

forms a reddish-brown powder soluble in A and B each denote a hydrogen or halogen water giving an orange colored solution atom attached to the phenyl nucleus, and R which on boiling with zinc dust produces a represents a sulfonated naphthyl nucleus violet coloration, and soluble in concentrated hi h contains a hydroxyl groupin ortho sulfuric acid giving a brownish-red solution osition to the azo group. The new dyestuffs which on dilution with ice changes'to' an orm orange to brown powders soluble 1n orange. It dyes wool from an acid bath'yelwater giving orange-yellow to reddish-brown lowish-brown shades which on after-chromsolutions which on boiling with zinc dust ing change to bluish-red tints which are of give violet colorations, and are soluble in conexcellent fastness to light, washing, fulling centrated sulfuric acid giving yellowish-red and potting. In dyeing wool interwoven to red solutions which on dilution with ice with silk, the silk is only slightly stained. change to various shades of orange. They If, in this,example,' 1-(2-chlor-5-sulfodye wool. from an acid bath various shades of phenyl) -3-methyl-5-pyrazolone be substibrown which on after-chroming change to tuted in equivalent quantity for the 1-(3'- yellowish-red to bluish-red tints of excellent sulfophenyl) -3-methyl-5-opyrazolone, there fastness to light,'washing, fulling and potis obtained a brownish powder which dyes.

ting. In dyeing wool interwoven with silk, wool in an acid bath yellowish-brown shades the silk is stained very little, if at all. which by after-chroming are converted into The following; specific example will further yellowish-blue red tints. illustrate the invention, but it is understood In an analogous manner, other valuable that the invention is not limited thereto. The monazo pyrazolone dyes are produced by parts are by weight. combining the same or another diazotized 0-. Earample.-5O parts (one mol) of the dry aminonaphthol sulfonic acid, for example, sodium salt of the diazo compound of 19- 1.2-aminonaphthol-6-sulfonic acid, 1.2-aminonaphthol-3.6-disulfonic acid, 2.1-aminona hthol-4-su1fon'ic acid, etc., on the one hand an the same or another 1-(3'-sulfophenyl)- 5-pyrazolone, for example, a 1- (2.5'-dichl 'or- 3-su lfophenyl) -5-pyrazolone, etc., on the other hand.

It will be understood that the pyrazolones contemplated in the resent invention carry a methyl or a carboxy group in the 3-position of the pyrazolone nucleus except where otherwise specified, and are ca able of combining with diazo compounds in t e i-positio'n.

mula I claim:

1. As new roducts, the monazo pyrazolone dyestuffs whichcorrespond with the following probable formula A I i I P wherein R signifies a 1- (3' sulfophenylg-iig methyl or carbox Liv-pyrazolone, A, an

each denotes. h rogen or a halo en atom attached to the p enyl nucleus, and re re sents a sulfonated naphthalene nucleus w iich contains a hydro 1 group in an ortho position to the azo bridge.

2. As new products, the monazo pyrazolone d estufis which correspond with the proba le formula I v wherein R signifies a 1-(3'-sulfophenyl) -3- methyl. or carboxyl-fi-pyrazolone, A and each denote a hydrogen or a halogen atom in the phenyl nucleus, and R denotes .a sulfonated naphthalene nucleus which contains a hydroxyl group in the ortho position tothe azobridge, said hydroxyl group adhering to one of the positions 1 and 2 in the naphthalene'nucleus and the azo bridge'adhering to the other position.

4. As new products, the monazo p razolone dyes which correspond with the pro able for wherein R signifies a 1-(3'-sulfophenyl)-3 methyl or carboxyl-5-pyrazolone, A and B eachdenote a hydrogen or a halogen atom in the phenyl nucleus, and R a sulfonated 2- hydroxynaphthalene nucleus where the azo bridge adheres to the 1-position of the naphthalene nucleus.

5. As new roducts, the monazo pyrazolone dyestuffs which correspond with the probable formula v I V yena-N som I wherein R si ifies a 1-(3'-sulfophenyl) -3- methyl or ca oxyl 5-pyrazolone, and A and B each denote a hydrogen or chlorine atom in the phenyl nucleus,

6. As new products, the monazo pyrazolone dye stufis which correspond withthe probable formula whereinfR signifies a 1-( 3'-sulfophenyl)-3-' meth l or car oxyl-5-pyrazolone, A denotes ahy rogen or a halogen atom in the phenyl nucleus, and R a sulfonated naphthalene nucleus which contains a hydroxyl group in an ortho position to the azo bridge.

7. As new roducts, the monazo pyrazolone dyestufls which correspond with-the probable formula V A-RN=NR wherein R signifies a1-(3-su1fophenyl)-3- methyl or carboxyl-5-pyrazolone, A denotes' ahydrogen or a halogen atom in the phenyl nucleus, and R a sulfonated naphthalene nucleus which contains a hydroxyl group in ortho position to the azo bridge, said hydroxyl group adhering to one of the positions 1 and 2- in the naphthalene nucleus and the azo bridge adhering to the other position.

8. As new products, the monazo pyrazolone dyestufls which correspondwith the probable formula I B wherein R signifies a 1-(3'-sulfophenyl)-3- ,methyl or carboxyl-5-pyrazolone, A denotes a hydrogen or a chlormeatom in the phenyl nucleus, and R a sulfonated 2-hydroxynap thalene nucleus where the azo bridge adheres to the 1-position of the "naphthalene nucleus.

9. As new products, the monazo pyrazolon dyestuffs which correspond with the probable formula wherein .R si ifies a 1-(3'-sulfophenyl)- -3- methyl or car 'notesa hydrogen or a chlorine atom attached xyl-5-pyrazolone and A deto the henyl nucleus.

10. s new dyestuffs, the 'fnonazo pyrazolone dyestuffs which correspond to the probable formula wherein R denotes a monosulfonated naphthalene nucleus which contains a hydroxyl group in ortho position to the azo bridge which adheres to the 1-position.

11. As a new product, the monazo pyrazolone dyestufi which corresponds with the probable formula 12. As new products, the monazo pyrazolone dyestuffs which correspond with the probable formula wherein A denotes a hydrogen or a. halogen atom, and R denotes a methyl or a carboxyl Y group.

13. As new products, the monazo pyrazolone dyestuffs which correspond with the probable formula A N N===C CHa CO-flH-N=N SOaH wherein A denotes a hydrogen or chlorine atom.

14. Material dyed claim 1. I V

15. Material dyed claim 2.

16. Material dyed claim 3.

dyed

dyed

dyed

dyed

with a dyestufl' of with a dyestuif with a dyestufli' 17. Material with a claim 4.

18. Material claim 5.

19. Material claim 6.

20. Material claim 7 21. Material claim 8.

22. Material claim 9.

23. Material claim 10.

dyestuif with a dyestufi' with a dyestufi with a dyestufl dyed with a dyestuif dyed with a dyestufl' dyed with a dyestuff of of I of 

